Carbonate Facilitated Mobilization of Uranium from Lacustrine Sediments under Anoxic Conditions.

Sorbed U(IV) species can be major products of U(VI) reduction in natural reducing environments as sediments and waterlogged soils. These species are considered more labile than crystalline U(IV) minerals, which could potentially influence uranium migration in natural systems subjected to redox oscillations. In this study, we examined the role of oxygen and carbonate on the remobilization of uranium from lake sediments, in which ∼70% of the 150-300 ppm U is under the form of mononuclear U(IV) sorbed species. Our results show that both drying and oxic incubation only slightly increase the amount of remobilized U after 8 days, compared to anoxic drying and anoxic incubation. In contrast, the amount of remobilized U increases with the quantity of added bicarbonate even under anoxic conditions. Moreover, U LIII-edge XANES data show that a significant amount of the solid U(IV) is mobilized in such conditions. Thermodynamic speciation calculations based on the supernatant composition indicates the predominance of aqueous UO2(CO3)34- and, to a lesser extent, CaUO2(CO3)32- complexes. These results suggest that monomeric U(IV) species could be oxidized into aqueous U(VI) carbonate complexes even under anoxic conditions via carbonate promoted oxidative dissolution, which emphasizes the need for considering such a process when modeling U dynamics in reducing environments.

Uranium(VI) Scavenging by Amorphous Iron Phosphate Encrusting Sphaerotilus natans Filaments.

U(VI) sorption to iron oxyhydroxides, precipitation of phosphate minerals, as well as biosorption on bacterial biomass are among the most reported processes able to scavenge U(VI) under oxidizing conditions. Although phosphates significantly influence bacterially mediated as well as iron oxyhydroxide mediated scavenging of uranium, the sorption or coprecipitation of U(VI) with poorly crystalline nanosized iron phosphates has been scarcely documented, especially in the presence of microorganisms. Here we show that dissolved U(VI) can be bound to amorphous iron phosphate during their deposition on Sphaerotilus natans filamentous bacteria. Uranium LIII-edge EXAFS analysis reveals that the adsorbed uranyl ions share an equatorial oxygen atom with a phosphate tetrahedron of the amorphous iron phosphate, with a characteristic U-P distance of 3.6 Å. In addition, the uranyl ions are connected to FeO6 octahedra with U-Fe distances at ~3.4 Å and at ~4.0 Å. The shortest U-Fe distance corresponds to a bidentate edge-sharing complex often reported for uranyl adsorption onto iron oxyhydroxides, whereas the longest U-Fe and U-P distances can be interpreted as a bidentate corner-sharing complex, in which two adjacent equatorial oxygen atoms are shared with the vertices of a FeO6 octahedron and of a phosphate tetrahedron. Furthermore, based on these sorption reactions, we demonstrate the ability of an attached S. natans biofilm to remove uranium from solution without any filtration step.

Moderate oxygen depletion as a factor favouring the filamentous growth of Sphaerotilus natans.

Sphaerotilus natans is a neutrophilic iron-related sheath-forming filamentous microorganism that presents dual morphotype: single cells and ensheathed cells forming filaments. As S. natans has been proposed as a sorbent for inorganic pollutants and it is occasionally involved in bulking episodes, elucidating factors affecting its filamentous growth is of crucial interest. The purpose of this work was to evaluate the effect of dissolved oxygen (DO) as a factor affecting S. natans filamentation from single cells. A method to quantify S. natans in its filamentous and single-cell morphotypes, based on a differential filtration procedure coupled with quantitative real-time PCR, was developed here. Scanning Electron Microscopy was used to validate the filtration step. Under actively aerated conditions (DO maintained at 7.6 ± 0.1 mg l(-1)), S. natans grew mainly as single cells throughout the experiment, while a depletion in DO concentration (to ~3 mg l(-1)) induced its filamentous growth. Indeed, when oxygen was reduced the proportion of single cells diminished from 83.3 ± 5.9 to 14.3 ± 3.4% while the filaments increased from 16.7 ± 5.9 to 85.7 ± 3.4%. Our results suggest that oxygen plays a key role in S. natans filamentation and contribute to better understanding of the filamentous proliferation of this bacterium. In addition, the proposed method will be helpful to evaluate other factors favouring filamentous growth.

Membrane lipid adaptation of soil Bacteroidetes isolates to temperature and pH.

3-hydroxy fatty acids (3-OH FAs) are characteristic components of the Gram-negative bacterial membrane, recently proposed as promising temperature and pH (paleo) proxies in soil. Nevertheless, to date, the relationships between the 3-OH FA distribution and temperature/pH are only based on empirical studies, with no ground truthing work at the microbial level. This work investigated the influence of growth temperature and pH on the lipid composition of three strains of soil Gram-negative bacteria belonging to the Bacteroidetes phylum. Even though non-hydroxy FAs were more abundant than 3-OH FAs in the investigated strains, our results suggest that 3-OH FAs are involved in the membrane adaptation of these bacteria to temperature. The strains shared a common adaptation mechanism to temperature, with a significant increase in the ratio of anteiso vs. iso or normal 3-OH FAs at lower temperature. In contrast with temperature, no common adaptation mechanism to pH was observed, as the variations in the FA lipid profiles differed from one strain to another. We suggest that models reconstructing environmental changes in soils should include the whole suite of 3-OH FAs present in the membrane of Gram-negative bacteria, as all of them could be influenced by temperature or pH at the microbial level.

Influence of microorganisms on uranium release from mining-impacted lake sediments under various oxygenation conditions.

Microbial processes can be involved in the remobilization of uranium (U) from reduced sediments under O2 reoxidation events such as water table fluctuations. Such reactions could be typically encountered after U-bearing sediment dredging operations. Solid U(IV) species may thus reoxidize into U(VI) that can be released in pore waters in the form of aqueous complexes with organic and inorganic ligands. Non-uraninite U(IV) species may be especially sensitive to reoxidation and remobilization processes. Nevertheless, little is known regarding the effect of microbially mediated processes on the behaviour of U under these conditions.

Early diagenesis of radium 226 and radium 228 in lacustrine sediments influenced by former mining sites.

Radium is a naturally occurring radioactive element commonly found at low levels in natural systems such as lacustrine or marine sediments. Anthropogenic activities including former uranium mining activities can lead to the dissemination of radium isotopes having high radiological toxicities, which potentially threaten the safety of nearby environments. Although radium mobility in oxidized environments is known to be largely governed by sorption/desorption onto Fe and Mn oxyhydroxides and coprecipitation with sulfate minerals (e.g. barite), little is known regarding its behavior under reducing conditions, which are the conditions typically encountered in organic-rich systems such as wetlands and lake sediments. The present study aims at understanding the behavior of long-lived radium isotopes (226Ra and 228Ra), during early diagenesis of lake sediments contaminated by former uranium mining activities. Solid and pore water concentrations of 226Ra and 228Ra were determined using ultra low background gamma spectrometry, which allowed improvement of detection limits and measurement accuracy. This study shows that the downcore distribution of radium isotopes is closely related to the reductive dissolution of iron and manganese oxyhydroxides below the sediment-water interface. The resulting diffusive fluxes of 226Ra and 228Ra (4.1 10-25 and 4.7 10-28 mol cm-2.s-1) are however significantly lower than other radium-impacted environments, such as uranium mill tailings pond and phosphate industry-impacted sediments, and are similar to those reported for natural marine environments. Hence, in the reduced lake sediments of Saint-Clement, the major fraction of radium is trapped by the solid phase, while early diagenesis only induces a slight mobility of this radioelement.

Effect of temperature on selenium removal from wastewater by UASB reactors.

The effect of temperature on selenium (Se) removal by upflow anaerobic sludge blanket (UASB) reactors treating selenate and nitrate containing wastewater was investigated by comparing the performance of a thermophilic (55 °C) versus a mesophilic (30 °C) UASB reactor. When only selenate (50 µM) was fed to the UASB reactors (pH 7.3; hydraulic retention time 8 h) with excess electron donor (lactate at 1.38 mM corresponding to an organic loading rate of 0.5 g COD L(-1) d(-1)), the thermophilic UASB reactor achieved a higher total Se removal efficiency (94.4 ± 2.4%) than the mesophilic UASB reactor (82.0 ± 3.8%). When 5000 µM nitrate was further added to the influent, total Se removal was again better under thermophilic (70.1 ± 6.6%) when compared to mesophilic (43.6 ± 8.8%) conditions. The higher total effluent Se concentration in the mesophilic UASB reactor was due to the higher concentrations of biogenic elemental Se nanoparticles (BioSeNPs). The shape of the BioSeNPs observed in both UASB reactors was different: nanospheres and nanorods, respectively, in the mesophilic and thermophilic UASB reactors. Microbial community analysis showed the presence of selenate respirers as well as denitrifying microorganisms.

Entrapped elemental selenium nanoparticles affect physicochemical properties of selenium fed activated sludge.

Selenite containing wastewaters can be treated in activated sludge systems, where the total selenium is removed from the wastewater by the formation of elemental selenium nanoparticles, which are trapped in the biomass. No studies have been carried out so far on the characterization of selenium fed activated sludge flocs, which is important for the development of this novel selenium removal process. This study showed that more than 94% of the trapped selenium in activated sludge flocs is in the form of elemental selenium, both as amorphous/monoclinic selenium nanospheres and trigonal selenium nanorods. The entrapment of the elemental selenium nanoparticles in the selenium fed activated sludge flocs leads to faster settling rates, higher hydrophilicity and poorer dewaterability compared to the control activated sludge (i.e., not fed with selenite). The selenium fed activated sludge showed a less negative surface charge density as compared to the control activated sludge. The presence of trapped elemental selenium nanoparticles further affected the spatial distribution of Al and Mg in the activated sludge flocs. This study demonstrated that the formation and subsequent trapping of elemental selenium nanoparticles in the activated sludge flocs affects their physicochemical properties.